KR20180039100A - film - Google Patents

Abstract

Wherein the outer layer comprises a polypropylene resin, the intermediate layer comprises a polypropylene resin and a hydrogenated block copolymer (a), the inner layer comprises a polypropylene resin, and the hydrogenated block copolymer (a) contains a conjugated diene compound as a main component (C) in the hydrogenated block copolymer (a), a polymer block (B) mainly comprising a conjugated diene compound, and a polymer block (S) comprising a vinyl aromatic compound as a main component. , The content of the polymer block (B) is 69 to 98 mass%, the content of the polymer block (S) is 1 to 20 mass%, the content of the vinyl block (C) And the hydrogenation block copolymer (a) has a hydrogenation rate of 80 mol% or more, the polymer block (B) has a vinyl bond amount before hydrogenation of 60 to 100 mol% It is a film.

Description

film

The present invention relates to a film.

BACKGROUND ART [0002] Polypropylene resins are widely used for packaging materials, machine parts, automobile parts and the like because they generally have excellent chemical resistance and mechanical properties.

In recent years, the development of non-halogen based transparent polymer materials has been progressing due to the necessity for environmental problems. Particularly, in the field of film, polypropylene resin is used, and the polypropylene resin is softened and made transparent And so on.

(B) a polybutadiene block segment (A) having a 1,4-bond content of 70% or more and a polybutadiene block segment (A) containing 70% by weight or more of a conjugated diene compound or a conjugated diene compound A random copolymer of a vinyl aromatic compound and a conjugated diene compound, which is a block copolymer comprising a block segment (B) having a conjugated diene compound portion having a vinyl bond content of 60% or more, wherein at least 80% of the double bonds of the conjugated diene portion (C) + (B) + (C) = 100% by weight) containing 0 to 98% by weight of a saturated hydrogenated diene polymer, and (C) A flexible molded article for use in the present invention.

Patent Literature 2 discloses a multi-layer laminate provided with a surface layer (II) on at least one side of a base layer (I), wherein the base layer (I) ((A) a polyolefin-based resin, (b) a conjugated diene, and (C) a polyolefin-based resin, wherein the surface layer (II) comprises 95 to 50/5 to 50 wt% A hydrogenated diene copolymer having a number average molecular weight of 50,000 to 700,000 and having a double bond in a conjugated diene part of the polymer saturated by 80% or more, (c) a poly A hydrogenated diene-based copolymer having a block in which a butadiene polymer is hydrogenated at an end, and at least one end thereof).

Japanese Patent Application Laid-Open No. 2000-93490 Japanese Patent Laid-Open No. 9-327893

It is required that transparency and flexibility are required for a molded article of a polypropylene resin composition used in a food packaging field, a medical (clothing) packaging field, and a medical (medical) field.

However, all of the molded articles described in Patent Document 1 and the multilayer laminate disclosed in Patent Document 2 still have room for improvement in transparency and flexibility.

Therefore, in the present invention, it is an object to provide a film having excellent transparency, flexibility, and balance of characteristics in consideration of the problems of the above-mentioned prior art.

The present inventors have intensively studied in order to solve the above problems, and as a result, they have found that the above problems can be solved by a film containing a hydrogenated block copolymer (a) having a specific structure, and have accomplished the present invention.

That is, the present invention is as follows.

〔One〕

At least an outer layer, an intermediate layer and an inner layer,

Wherein said outer layer comprises a polypropylene resin,

Wherein the intermediate layer comprises a polypropylene resin and a hydrogenated block copolymer (a)

Wherein the inner layer comprises a polypropylene resin,

The hydrogenated block copolymer (a)

A polymer block (C) mainly comprising a conjugated diene compound,

A polymer block (B) mainly comprising a conjugated diene compound,

The polymer block (S) containing a vinyl aromatic compound as a main component

Lt; / RTI >

Wherein the content of the polymer block (C) having the conjugated diene compound as a main component in the hydrogenated block copolymer (a) is 1 to 30 mass% and the content of the polymer block (B) containing the conjugated diene compound as the main component is 69 To 98% by mass, the content of the polymer block (S) containing the vinyl aromatic compound as a main component is 1 to 20% by mass,

Wherein the amount of the vinyl block before hydrogenation of the polymer block (C) mainly composed of the conjugated diene compound is 1 to 25 mol%, the amount of vinyl bonds of the polymer block (B) mainly composed of the conjugated diene compound before hydrogenation is 60 to 100 mol% Wherein the hydrogenated block copolymer (a) has a hydrogenation rate of 80 mol% or more,

film.

〔2〕

Wherein the content of the polymer block (C) containing the conjugated diene compound as a main component in the hydrogenated block copolymer (a) is 3 to 13 mass% and the content of the polymer block (B) 96 mass%, the content of the polymer block (S) containing the vinyl aromatic compound as a main component is 3 to 13 mass%

The total content of the polymer block (C) containing the conjugated diene compound as a main component and the polymer block (S) containing the vinyl aromatic compound as a main component is 6 to 26% by mass,

The hydrogenated block copolymer (a) has a hydrogenation rate of 90 mol% or more.

[3]

At least an outer layer, an intermediate layer and an inner layer,

Wherein said outer layer comprises a polypropylene resin,

Wherein the intermediate layer comprises a polypropylene resin and a hydrogenated block copolymer (a)

Wherein the inner layer comprises a polypropylene resin,

Wherein the content of the vinyl aromatic compound monomer unit in the hydrogenated block copolymer (a) is 3 to 13 mass%

Wherein the hydrogenation block copolymer (a) has a hydrogenation rate of 90 mol%

The amount of butylene and / or propylene in the hydrogenated block copolymer (a) is 60 to 85 mol% based on 100 mol% of the total of the conjugated diene compound units,

The hydrogenated block copolymer (a) has a peak of crystallization at 0 to 60 캜,

Wherein the hydrogenated block copolymer (a) has a crystallization calorie of 1.0 to 8.0 J / g,

Wherein the hydrogenated block copolymer (a) has a Shore A hardness of 25 to 55,

film.

〔4〕

The film according to any one of [1] to [3], wherein the thickness of the outer layer is 5 to 50 μm, the thickness of the intermediate layer is 100 to 200 μm, and the thickness of the inner layer is 5 to 50 μm.

[5]

Wherein the outer layer comprises the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1), provided that the block copolymer (b1) does not contain the polymer block (C) containing the conjugated diene compound as a main component ),

Wherein the hydrogenated block copolymer (b1) comprises a polymer block (B1) composed mainly of a conjugated diene compound and a polymer block (S1) composed mainly of a vinyl aromatic compound,

Wherein the content of the polymer block (B1) having the conjugated diene compound as a main component in the hydrogenated block copolymer (b1) is 75 to 92 mass%, the content of the polymer block (S1) containing the vinyl aromatic compound as the main component is 8 To 25% by mass,

Wherein the hydrogenated block copolymer (b1) has a hydrogenation degree of not less than 80 mol%, and the hydrogenated block copolymer (b1) has a hydrogenation amount of not less than 40 mol%

The content of the polypropylene resin in the outer layer is 60 to 100 mass%

Wherein the content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the outer layer is 0 to 40 mass%

The film according to any one of [1] to [4].

[6]

Wherein the inner layer comprises the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the block copolymer (b1) does not contain the polymer block (C) mainly comprising the conjugated diene compound ),

Wherein the hydrogenated block copolymer (b1) comprises a polymer block (B1) composed mainly of a conjugated diene compound and a polymer block (S1) composed mainly of a vinyl aromatic compound,

Wherein the content of the polymer block (B1) having the conjugated diene compound as a main component in the hydrogenated block copolymer (b1) is 75 to 92 mass%, the content of the polymer block (S1) containing the vinyl aromatic compound as the main component is 8 To 25% by mass,

Wherein the hydrogenated block copolymer (b1) has a hydrogenation degree of not less than 80 mol%, and the hydrogenated block copolymer (b1) has a hydrogenation amount of not less than 40 mol%

The content of the polypropylene resin in the inner layer is 50 to 95 mass%

The film according to any one of [1] to [4], wherein the content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the inner layer is 5 to 50 mass%.

[7]

The hydrogenated block copolymer (a)

(A) in the polymer block (B) containing at least two polymer blocks (B) containing the conjugated diene compound as a main component and having the conjugated diene compound as a main component, Wherein the content of the polymer block (B-1) is 1 to 10% by mass of the hydrogenated block copolymer (a)

The film according to any one of [1] to [6].

〔8〕

Wherein the outer layer further comprises a hydrogenated block copolymer (b2)

Wherein the hydrogenated block copolymer (b2) comprises a polymer block (B2) composed mainly of a conjugated diene compound and a polymer block (S2) composed mainly of a vinyl aromatic compound,

Wherein the content of the polymer block (B2) mainly composed of the conjugated diene compound in the hydrogenated block copolymer (b2) is 75 to 92 mass% and the content of the polymer block (S2) composed mainly of the vinyl aromatic compound is 8 To 25% by mass,

Wherein the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%, and the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%

The hydrogenated block copolymer (b2)

(B2) in the polymer block (B2) containing at least two polymer blocks (B2) composed mainly of the conjugated diene compound in the molecule, and having a conjugated diene compound as a main component, Wherein the content of the polymer block (B-2) is 1 to 10% by mass in the hydrogenated block copolymer,

The film according to any one of [1] to [7].

[9]

Wherein the inner layer further comprises a hydrogenated block copolymer (b2)

Wherein the hydrogenated block copolymer (b2) comprises a polymer block (B2) composed mainly of a conjugated diene compound and a polymer block (S2) composed mainly of a vinyl aromatic compound,

Wherein the content of the polymer block (B2) mainly composed of the conjugated diene compound in the hydrogenated block copolymer (b2) is 75 to 92 mass% and the content of the polymer block (S2) composed mainly of the vinyl aromatic compound is 8 To 25% by mass,

Wherein the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%, and the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%

The hydrogenated block copolymer (b2)

(B2) in the polymer block (B2) containing at least two polymer blocks (B2) composed mainly of the conjugated diene compound in the molecule, and having a conjugated diene compound as a main component, Wherein the content of the polymer block (B-2) is 1 to 10% by mass in the hydrogenated block copolymer,

The film according to any one of [1] to [8].

[10]

The film according to any one of [1] to [9], wherein the hydrogenated block copolymer (a) has a weight average molecular weight (Mw) of 100,000 to 300,000.

[11]

Wherein the hydrogenated block copolymer (a) has a weight average molecular weight (Mw) of 100,000 to 300,000 and a ratio (Mw / Mn) of the weight average molecular weight (Mw) (Mn) of from 1.01 to 1.30.

[12]

Wherein the integral elution amount at -20 캜 or lower as measured by cross fractionation chromatography (CFC) is 0.1% or more and less than 40% of the total integral elution amount, and the integral elution amount in the range of more than -20 캜 and less than 60 캜 is the total integral The film according to any one of [1] to [11], wherein the elution amount is 20% or more and less than 95%, and the integral elution amount in the range of 60 ° C or more and 150 ° C or less is 5% or more and less than 70% or less of the total integral elution amount.

[13]

The film according to any one of [1] to [12], wherein the molecular weight distribution (Mw / Mn) of the eluted component in the range of 10 ° C or more and less than 60 ° C as measured by cross fractionation chromatography (CFC) is 1.05 or more and 1.50 or less.

According to the present invention, it is possible to provide a film having excellent transparency, flexibility, and balance of characteristics thereof.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, specific details for carrying out the present invention (hereinafter simply referred to as " present embodiment ") will be described in detail. The following embodiments are illustrative of the present invention and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the present invention.

〔film〕

The film of this embodiment has at least an outer layer, an intermediate layer and an inner layer.

Here, the "outer layer" and "inner layer" are surface layers laminated on both surfaces of the "intermediate layer", and the "outer layer" refers to the outermost layer when actually provided for use.

The outer layer comprises a polypropylene resin.

The intermediate layer includes a polypropylene resin and a hydrogenated block copolymer (a).

The inner layer comprises a polypropylene resin.

By having such a constitution, a film excellent in transparency and flexibility can be obtained.

(Hydrogenated block copolymer (a))

The hydrogenated block copolymer (a)

A polymer block (C) mainly comprising a conjugated diene compound,

A polymer block (B) mainly comprising a conjugated diene compound,

The polymer block (S) containing a vinyl aromatic compound as a main component

.

Wherein the content of the polymer block (C) having the conjugated diene compound as a main component in the hydrogenated block copolymer (a) is 1 to 30 mass% and the content of the polymer block (B) containing the conjugated diene compound as the main component is 69 To 98% by mass, the content of the polymer block (S) containing the vinyl aromatic compound as a main component is 1 to 20% by mass,

Wherein the amount of the vinyl block before hydrogenation of the polymer block (C) mainly composed of the conjugated diene compound is 1 to 25 mol%, the amount of vinyl bonds of the polymer block (B) mainly composed of the conjugated diene compound before hydrogenation is 60 to 100 mol% The hydrogenation block copolymer has a hydrogenation rate of 80 mol% or more.

Here, the term " as a main component " means that the target monomer unit is contained in an amount of 50 mass% or more in the target polymer block.

The content of the conjugated diene compound in each of the polymer block (C) and the polymer block (B) containing the conjugated diene compound as a main component is preferably 60% by mass or more, more preferably 60% by mass or more, It is preferably at least 70 mass%, more preferably at least 80 mass%, even more preferably at least 90 mass%.

From the viewpoints of the mechanical strength and the impact resistance of the film of the present embodiment, the content of the vinyl aromatic compound in the polymer block (S) containing a vinyl aromatic compound as a main component is preferably at least 60 mass%, more preferably at least 70 By mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more.

In the present embodiment, the name of each monomer unit constituting the block copolymer is to follow the naming of a monomer derived from the monomer unit.

For example, " vinyl aromatic monomer unit " means a structural unit of a polymer resulting from polymerization of a vinyl aromatic compound as a monomer, and the structure thereof is such that two carbon atoms of a substituted ethylene group derived from a substituted vinyl group It is a molecular structure that is a binding site.

The term " conjugated diene compound monomer unit " means a constituent unit of a polymer resulting from polymerization of a conjugated diene compound as a monomer, and the structure thereof is such that two carbon atoms of an olefin derived from a conjugated diene compound monomer Lt; / RTI >

Quot; amount of vinyl bond before hydrogenation " in the polymer block (C) or (B) having a conjugated diene compound as a main component means the amount of vinyl bond before hydrogenation, ) And a total amount of 1,2-bond (when the polymer is inserted into the polymer as a 3,4-bond, the total amount of 1,2-bond and 3,4-bond) (The total amount of 1,2-bond and 3,4-bond when molybdenum is inserted into the polymer as a 3,4-bond) (mol%).

The amount of vinyl bond can be measured by nuclear magnetic resonance spectrum analysis (NMR).

The content of the polymer block (C) containing the conjugated diene compound as a main component in the hydrogenated block copolymer (a) is 1 to 30% by mass.

The content of the polymer block (C) containing the conjugated diene compound as the main component in the hydrogenated block copolymer (a) is preferably from 2 to 20% by mass from the viewpoint of transparency and flexibility of the film of the present embodiment, Preferably 2 to 15% by mass, and more preferably 3 to 13% by mass.

The amount of the vinyl block before hydrogenation of the polymer block (C) containing the conjugated diene compound as a main component is 1 to 25 mol%.

The amount of vinyl bonds before hydrogenation of the polymer block (C) containing the conjugated diene compound as a main component is preferably 3 to 23 mol%, more preferably 5 to 20 mol%, in view of the water vapor barrier property of the film of the present embodiment. to be.

The vinyl bonding amount of the polymer block (C) containing the above-mentioned conjugated diene compound as a main component before hydrogenation can be specifically measured by the method described in the following Examples.

The amount of the vinyl bond can be controlled by using a polarizing compound or a vinylating agent such as a Lewis base, an ether or an amine.

The content of the polymer block (B) having the conjugated diene compound as a main component in the hydrogenated block copolymer (a) is 69 to 98% by mass.

The content of the polymer block (B) containing the conjugated diene compound as a main component is preferably from 70 to 97 mass%, more preferably from 73 to 96 mass%, from the viewpoint of transparency and flexibility of the film of the present embodiment , And more preferably from 74 to 96 mass%.

The amount of vinyl bonds of the polymer block (B) containing the conjugated diene compound as a main component before hydrogenation is 60 to 100 mol%.

The vinyl bond amount of the polymer block (B) containing the conjugated diene compound as a main component before hydrogenation is preferably 63 to 98 mol%, more preferably 65 to 95 mol%, from the viewpoint of transparency and flexibility of the film of the present embodiment %to be.

The vinyl bonding amount of the polymer block (B) containing the above-mentioned conjugated diene compound as a main component before hydrogenation can be specifically measured by a method described in Examples described later.

The amount of the vinyl bond can be controlled by using a polarizing compound or a vinylating agent such as a Lewis base, an ether or an amine.

In the film of the present embodiment, the conjugated diene compound used in the polymer blocks (C) and (B) in the hydrogenated block copolymer (a) is a diolefin having a pair of conjugated double bonds.

Examples of the diolefins include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3- Pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and parnesene.

Particularly, typical diolefins include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more.

In the film of the present embodiment, the vinyl aromatic compound used in the polymer block (S) in the hydrogenated block copolymer (a) is not limited to the following examples, and examples thereof include styrene, Vinyl aromatic compounds such as methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene and N, N-diethyl-p-aminoethylstyrene.

Of these, styrene,? -Methylstyrene and 4-methylstyrene are preferably used from the viewpoints of availability and productivity. Particularly preferred is styrene. The polymer block (S) may be composed of one kind of vinyl aromatic compound unit or two or more kinds thereof.

The conjugated diene compound and the vinyl aromatic compound are also applicable to the hydrogenated block copolymer (b1) and the hydrogenated block copolymer (b2) described later.

The content of the polymer block (S) based on the vinyl aromatic compound in the hydrogenated block copolymer (a) is 1 to 20% by mass.

The content of the polymer block (S) containing a vinyl aromatic compound as a main component is preferably from 2 to 18 mass%, more preferably from 3 to 15 mass%, further preferably from 3 to 15 mass% from the viewpoints of transparency and flexibility of the film of the present embodiment And preferably 3 to 13 mass%.

The hydrogenation rate of the hydrogenated block copolymer (a), that is, the hydrogenation rate of the entire conjugated diene compound unit contained in the hydrogenated block copolymer (a) is 80 mol% or more.

The hydrogenation rate is preferably 85 mol% or more, and more preferably 90 mol% or more, from the viewpoints of transparency, flexibility, and water vapor barrier property of the film of the present embodiment.

The hydrogenation ratio of the total unsaturated group units contained in the conjugated diene monomer units of the hydrogenated block copolymer (a) can be measured by nuclear magnetic resonance spectrum analysis (NMR), and specifically, Can be measured by a method.

When the hydrogenation degree of the hydrogenated block copolymer (a) is 80 mol% or more, the crystallinity of the polymer block (C) becomes high and the transparency, flexibility, hydrogen barrier property of the molded resin composition obtained by mixing the hydrogenated block copolymer (a) with the polypropylene resin The property becomes good.

When the resin composition obtained by mixing the hydrogenated block copolymer (a) with the polypropylene resin is used as the material of the film, the solubility parameters of the polymer block (B) and the polypropylene resin are close to each other, (a) is improved, flexibility and transparency are improved.

The hydrogenation rate can be controlled by, for example, the amount of catalyst upon hydrogenation, and the rate of hydrogenation can be controlled by, for example, the amount of catalyst at the time of hydrogenation, the amount of hydrogen feed, the pressure and the temperature.

Further, in the film of this embodiment,

The content of the vinyl aromatic compound monomer unit in the hydrogenated block copolymer (a) is 3 to 13% by mass,

The hydrogenation degree of the hydrogenated block copolymer (a) was 90 mol%

The amount of butylene and / or propylene in the hydrogenated block copolymer (a) is 60 to 85 mol% based on the total 100 mol% of the conjugated diene compound units,

The hydrogenated block copolymer (a) has a peak of crystallization at 0 to 60 캜,

The crystallization heat of the hydrogenated block copolymer (a) is 1.0 to 8.0 J / g,

And the Shore A hardness of the hydrogenated block copolymer (a) is from 25 to 55. [

Here, the butylene amount and the propylene amount mean respectively a monomer unit of butadiene and isoprene after hydrogenation.

The amount of butylene and / or propylene, the peak temperature of crystallization, the heat of crystallization, and the Shore A hardness can be measured by, for example, as described above, as the hydrogenated block copolymer (a) Can be controlled by using a hydrogenated block copolymer containing a block (C), a polymer block (B) mainly composed of a conjugated diene compound and a polymer block (S) composed mainly of a vinyl aromatic compound.

The amount of butylene and / or propylene, the peak temperature of crystallization, the heat of crystallization, and the Shore A hardness can be measured specifically by the method described in Examples described later.

In the film of the present embodiment, it is preferable that the thickness of the outer layer is 5 to 50 mu m, the thickness of the intermediate layer is 100 to 200 mu m, and the thickness of the inner layer is 5 to 50 mu m.

When each layer is in the above numerical range, good flexibility, impact resistance and heat sealability are obtained.

The thickness of the outer layer is more preferably 10 to 40 占 퐉, and further preferably 15 to 35 占 퐉.

The thickness of the intermediate layer is more preferably 110 to 190 占 퐉, and still more preferably 120 to 180 占 퐉.

The thickness of the inner layer is more preferably from 10 to 45 mu m, and further preferably from 15 to 40 mu m.

In general, a sheet-shaped formed article having a thickness of 0.005 mm or more and less than 0.25 mm is referred to as a film, and a sheet-shaped formed article having a thickness of 0.25 mm or more and 50 mm or less is referred to as a sheet. In this specification, the term " do.

The film of this embodiment has an integral elution amount of -20 占 폚 or less as measured by cross fractionation chromatography (hereinafter referred to as "CFC") of 0.1% or more and less than 40% of the total integral elution amount, Of the total integral elution amount is not less than 20% and not more than 95% of the total integral elution amount, and the integral elution amount in the range of 60 占 폚 to 150 占 폚 is preferably not less than 5% and less than 70% of the total integral elution amount.

By having the above-described constitution, a film excellent in transparency, flexibility, heat sealability, impact resistance and balance of characteristics thereof can be obtained.

From the viewpoints of transparency, flexibility, heat sealability, impact resistance and balance of characteristics thereof, the integral elution amount at -20 캜 or lower is more preferably 2% or more and less than 30%, more preferably 3% or more and less than 20% Is more preferable. It is more preferable that the integral elution amount in the range of more than -20 DEG C to less than 60 DEG C is 10% or more and less than 50%, more preferably 20% or more and less than 45% of the total integral elution amount. The integral elution amount in the range of 60 占 폚 to 150 占 폚 is more preferably 50% or more and less than 90%, and still more preferably 55% or more and less than 80% of the total integral elution amount.

The CFC elution amount can be controlled by adjusting the proportion of the polymer block (C), (B), the proportion of the hydrogenated block copolymer (a1), and the type of the polypropylene resin. The CFC elution amount can be measured by a method described in Examples to be described later.

It is also possible to collect the components in a range of -20 占 폚 or lower, a range of higher than -20 占 폚 and lower than 60 占 폚, a range of higher than or equal to 60 占 폚 and 150 占 폚 or lower, The content of vinyl aromatic units, the degree of hydrogenation, the amount of butylene and / or the amount of propylene, the crystallization peak temperature and crystallization heat, and Shore A hardness can be measured. Particularly, the hydrogenated block copolymer (a) is contained in a range of more than -20 ° C to less than 60 ° C.

It is preferable that the molecular weight distribution (Mw / Mn) of the eluted component in the range of 10 占 폚 or more and less than 60 占 폚 as measured by cross fractionation chromatography (CFC) is 1.05 or more and 1.50 or less.

The molecular weight distribution (Mw / Mn) can be specifically measured by the method described in the following examples.

The hydrogenated block copolymer (a) includes, for example, those having a structure represented by the following general formula.

(CB) _n- S

(CBS) _n

(CBS) _n - (B-1)

(CBS- (B-1)) _n

(CBS) _m -X

(CBS- (B-1)) _m- X

In the above general formulas, C, B and S each represent a polymer block (C) mainly comprising a conjugated diene compound, a polymer block (B) comprising a conjugated diene compound as a main component, a polymer block S).

(B-1) existing at the end of the hydrogenated block copolymer (a) in the polymer block (B) containing a conjugated diene compound as a main component .

n is an integer of 1 or more, preferably 1 to 6;

m is an integer of 2 or more, preferably 2 to 6;

X represents a bifunctional coupling agent moiety or a polyfunctional initiator moiety.

The hydrogenated block copolymer (a) is preferably a polymer represented by the structural formula of C-B-S, C-B-S- (B-1).

Examples of the bifunctional coupling agent include, but are not limited to, dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; And acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate and phthalic acid esters.

The polyfunctional coupling agent having three or more functional groups is not limited to the following examples, and examples thereof include polyvalent epoxy compounds such as trivalent or higher polyalcohols, epoxidized soybean oil, and diglycidyl bisphenol A; A halogenated silicon compound represented by the formula R ¹ _(4-n) SiX _n (wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is halogen and n is an integer of 3 or 4) .

Examples of the halogenated silicon compound include, but are not limited to, methyl silyl trichloride, t-butyl silyl trichloride, silicon tetrachloride, and bromides thereof.

Examples of the halogenated tin compound include, but are not limited to, polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Further, dimethyl carbonate, diethyl carbonate and the like can also be used.

In the above general formulas, the vinyl aromatic compound monomer units in the polymer block (C), the polymer block (B) and the polymer block (S) may be uniformly distributed or may be distributed in a tapered form. When the polymer block (C), the polymer block (B) and the polymer block (S) are a copolymer block of a vinyl aromatic monomer unit and a conjugated diene monomer unit, the vinyl aromatic monomer unit in the copolymer block A plurality of uniformly distributed portions and / or a plurality of distributed tapered portions may be present. In the copolymer block portion, a plurality of portions having different contents of vinyl aromatic compound monomer units may coexist.

The structure of the hydrogenated block copolymer (a), the hydrogenated block copolymer (b1) described later, and the hydrogenated block copolymer (b2) is not particularly limited and may take any form such as linear, branched, radial, However, it can be a preferable structure depending on desired physical properties and the like.

From the viewpoint of performance imparted to the film of the present embodiment, namely, transparency, flexibility, and good balance of properties thereof, the hydrogenated block copolymer (a) is a polymer block (B) containing the conjugated diene compound as a main component, Wherein the content of the polymer block (B-1) present at the end of the hydrogenated block copolymer (a) in the polymer block (B) containing two or more of the hydrogenated block copolymers (B) it is preferably 1 to 10% by mass in a).

The content of the polymer block (B-1) present at the terminal of the hydrogenated block copolymer (a) can be controlled by the amount of the conjugated diene compound added.

The content of the polymer block (B-1) present at the terminal of the hydrogenated block copolymer (a) is preferably from 2 to 8% by mass, more preferably from 2 to 6% by mass in the hydrogenated block copolymer (a) More preferable.

The weight average molecular weight (Mw) (hereinafter, also referred to as " Mw ") of the hydrogenated block copolymer (a) is preferably 100,000 to 300,000.

The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) is preferably from 110,000 to 290,000, more preferably from 12,000 to 300,000, from the viewpoints of transparency, flexibility, and physical properties balance of the film of the present embodiment. To 28,000.

The Mw of the hydrogenated block copolymer (a) can be controlled by the amount of the polymerization initiator.

The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) is determined by measuring the molecular weight of the peak of the chromatogram obtained by measurement by GPC with a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from measurement of standard polystyrene on the market, (Mw) calculated on the basis of the weight average molecular weight (Mw).

The ratio (Mw) / (Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the hydrogenated block copolymer (a) is preferably 1.01 to 1.30.

Specifically, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by the method described in Examples to be described later.

(Production method of hydrogenated block copolymer (a)) [

Generally, the hydrogenated block copolymer (a) can be produced by carrying out polymerization of a conjugated diene compound monomer and a vinyl aromatic compound monomer using an organic alkali metal compound as a polymerization initiator in an organic solvent, and then conducting a hydrogenation reaction .

The form of the polymerization may be a batch polymerization, a continuous polymerization, or a combination thereof.

From the viewpoint of obtaining a block copolymer having a narrow molecular weight distribution and a high strength, a batch polymerization method is preferable.

The polymerization temperature is generally 0 to 150 占 폚, preferably 20 to 120 占 폚, and more preferably 40 to 100 占 폚.

The polymerization time varies depending on the target polymer, usually 24 hours or less, preferably 0.1 to 10 hours. And more preferably 0.5 to 3 hours from the viewpoint of obtaining a block copolymer having a narrow molecular weight distribution and a high strength.

The atmosphere of the polymerization system is not particularly limited so long as it is a pressure range sufficient to maintain the nitrogen and the solvent in a liquid state.

It is preferable that impurities such as water, oxygen, carbonic acid gas and the like are not present in the polymerization system to inactivate the polymerization initiator and the living polymer.

Examples of the organic solvent include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane; Alicyclic hydrocarbons such as cyclohexane, cycloheptane and methylcyclopentane; And aromatic hydrocarbons such as benzene, xylene, toluene and ethylbenzene.

As the organic alkali metal compound which is a polymerization initiator, an organic lithium compound is preferable. The organic lithium compound is not limited to the following, but for example, an organic monolithium compound, an organic di-lithium compound, an organic poly-lithium compound and the like are used.

Examples of the organic lithium compound include, but are not limited to, lithium, lithium, lithium, lithium, , Butadienyl lithium, and isopropenyldilithium. Of these, n-butyllithium and sec-butyllithium are preferable from the viewpoint of polymerization activity.

The amount of the organic alkali metal compound to be used as the polymerization initiator varies depending on the molecular weight of the target block copolymer, but it is preferably in the range of 0.01 to 0.5 phm (mass part per 100 mass parts of the monomer), more preferably 0.03 to 0.3 more preferably in the range of 0.05 to 0.15 phm, and still more preferably in the range of 0.05 to 0.15 phm.

The amount of vinyl bonding of the polymer block (B) and the polymer block (C) contained in the hydrogenated block copolymer (a) can be controlled by using a Lewis base, for example, a compound such as an ether or an amine as a vinylating agent. The amount of the vinylating agent to be used can be adjusted depending on the desired amount of vinyl bonding.

Further, by adding the vinylating agent and the metal alkoxide described below to two or more conditions separately, a polymer block having a different vinyl bonding amount can be produced from a polymer block mainly comprising a conjugated diene compound.

Examples of the vinylating agent include, but are not limited to, ether compounds, ether compounds having two or more oxygen atoms, and tertiary amine compounds.

Examples of the tertiary amine compound include, but are not limited to, pyridine, N, N, N ', N'-tetramethylethylenediamine, tributylamine, tetramethylpropanediamine, And bis [2- (N, N-dimethylamino) ethyl] ether.

These may be used alone, or two or more kinds may be used in combination.

As the tertiary amine compound, a compound having two amines is preferable. Among them, those having a structure showing symmetry in the molecule are more preferable, and N, N, N ', N'-tetramethylethylenediamine and bis [2- (N, N- dimethylamino) ethyl] ether And 1,2-dipiperidinoethane are more preferable.

In the present embodiment, the hydrogenated block copolymer may be copolymerized under the coexistence of the above-mentioned vinylating agent, organic lithium compound and alkaline metal alkoxide. Here, the alkali metal alkoxide is a compound represented by the general formula MOR (wherein M is an alkali metal and R is an alkyl group).

The alkali metal of the alkali metal alkoxide is preferably sodium or potassium from the viewpoints of a high vinyl bond amount, a narrow molecular weight distribution, a high polymerization rate and a high blocking ratio.

The alkali metal alkoxide is not particularly limited but is preferably a sodium alkoxide, lithium alkoxide or potassium alkoxide having an alkyl group having 2 to 12 carbon atoms, more preferably an alkoxy group having an alkyl group having 3 to 6 carbon atoms Sodium alkoxide or potassium alkoxide, and more preferably sodium-t-butoxide, sodium-t-pentoxide, potassium-t-butoxide and potassium-t-pentoxide.

Of these, sodium-alkoxide sodium-t-butoxide and sodium-t-pentoxide are even more preferred.

In the polymerization step of the hydrogenated block copolymer of the present embodiment, when the polymerization is carried out in the presence of the vinylating agent, the organic lithium compound and the alkali metal alkoxide, the molar ratio of the vinylating agent and the organic lithium compound (vinylating agent / organolithium compound) , And the molar ratio of the alkali metal alkoxide and the organolithium compound (alkali metal alkoxide / organic lithium compound) is preferably in the following molar ratio.

When the vinylating agent / organolithium compound is in the range of 0.2 to 3.0

When the alkali metal alkoxide / organic lithium compound is 0.01 to 0.3

The molar ratio of the vinylating agent / organolithium compound is preferably 0.2 or more from the viewpoint of high vinyl bonding amount and high polymerization rate, and is preferably less than 3.0 from the viewpoint of obtaining a narrow molecular weight distribution and a high hydrogenation activity.

The molar ratio of the alkali metal alkoxide / organic lithium compound is preferably 0.01 or more in view of high vinyl bonding amount, high polymerization rate and high blocking ratio, and is preferably 0.3 or less from the viewpoint of obtaining a narrow molecular weight distribution and a high hydrogenation activity .

As a result, the polymerization rate can be improved, the vinyl bonding amount of the desired hydrogenated block copolymer can be increased, the molecular weight distribution can be narrowed, and further the block ratio tends to be improved. As a result, the performance imparted to the polypropylene resin composition comprising the hydrogenated block copolymer (a) and the polypropylene resin, that is, flexibility and transparency tends to be better.

The molar ratio of the vinylating agent / organic lithium compound in the polymerization step is more preferably 0.8 or more from the viewpoint of high vinyl bonding amount and high polymerization rate, more preferably 2.5 or less from the viewpoint of narrow molecular weight distribution and high hydrogenation activity , And more preferably in the range of 1.0 to 2.0.

The molar ratio of the alkali metal alkoxide / organolithium compound is more preferably 0.02 or more from the viewpoint of high vinyl bonding amount, high polymerization rate and high blocking ratio, and 0.2 or less from the viewpoint of narrow molecular weight distribution and high hydrogenation activity More preferably 0.03 or more and 0.1 or less, still more preferably 0.03 or more and 0.08 or less.

The molar ratio of the alkali metal alkoxide / vinylating agent is preferably 0.010 or more from the viewpoints of high vinyl bonding amount, high polymerization rate and high block ratio, and from the viewpoint of achieving a narrow molecular weight distribution and obtaining a high hydrogenation activity More preferably 0.012 or more and 0.080 or less, still more preferably 0.015 or more and 0.06 or less, still more preferably 0.015 or more and 0.05 or less.

As a method for producing a polymer block having a different vinyl bonding amount in a polymer block mainly composed of a conjugated diene compound, a method of using a deflocculating agent for a vinylating agent can be used.

As the deflocculating agent, there may be mentioned alkyl metal compounds, alkyl aluminum having 1 to 20 carbon atoms per alkyl substituent group, zinc and magnesium, and mixtures thereof.

The hydrogenation method for producing the hydrogenated block copolymer (a) is not particularly limited. For example, hydrogen may be supplied to the obtained block copolymer in the presence of a hydrogenation catalyst to hydrogenate the hydrogenated block copolymer to obtain a conjugated diene compound unit A hydrogenated block copolymer in which a double bond residue is hydrogenated can be obtained.

The hydrogenation rate can be controlled by, for example, the amount of catalyst upon hydrogenation, and the rate of hydrogenation can be controlled by, for example, the amount of catalyst at the time of hydrogenation, the amount of hydrogen feed, the pressure and the temperature.

By pelletizing the hydrogenated block copolymer (a), pellets of the hydrogenated block copolymer (a) can be produced.

Examples of the pelletization method include a method in which a hydrogenated block copolymer is extruded from a uniaxial or biaxial extruder into a strand shape and cut in water by a rotating blade provided on the front side of the die; A method in which a hydrogenated block copolymer is extruded from a uniaxial or biaxial extruder into a strand shape, cooled or cooled by air, and then cut by a strand cutter; An open roll, a Banbury mixer, and then forming the sheet into a sheet by a roll, cutting the sheet into a rectangular shape, and then cutting the sheet into cubic pellets with a pelletizer.

The size and shape of the pelletized molded product of the hydrogenated block copolymer (a) are not particularly limited.

The pellets of the hydrogenated block copolymer may be blended with a pellet-blocking agent for the purpose of preventing pellet blocking if necessary.

Examples of the pellet-blocking agent include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bisstearylamide, talc, and amorphous silica.

From the viewpoint of transparency of the film of the present embodiment, calcium stearate, polyethylene and polypropylene are preferable.

The preferable amount of the pellet blocking agent is 200 to 8000 ppm based on the hydrogenated block copolymer (a). The more preferable amount is 300 to 7000 ppm with respect to the hydrogenated block copolymer (a).

The pellet-blocking agent is preferably blended in a state adhered to the surface of the pellet, but may be contained in the pellet to some extent.

(Polypropylene resin)

Examples of the polypropylene resin include a random polypropylene resin, a homopolypropylene resin, and a block polypropylene resin.

The polypropylene resin is preferably a random polypropylene resin.

Here, the term " random " in the random polypropylene means that propylene and a monomer other than propylene are copolymerized, and monomers other than propylene are randomly introduced into the propylene chain, and substantially no monomer other than propylene is chain-connected.

The random polypropylene is not particularly limited as long as the propylene unit content is less than 99.5% by mass. Preferable examples of the random polypropylene include a random copolymer of propylene and ethylene or a random copolymer of propylene and an? -Olefin having 4 to 20 carbon atoms.

When a random copolymer of propylene and ethylene or a random copolymer of propylene and an? -Olefin having 4 to 20 carbon atoms is used as the random polypropylene, the flexibility, transparency and impact resistance tend to be better.

Examples of the? -olefin include, but are not limited to, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, -Heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Preferred is an? -Olefin having 2 to 8 carbon atoms, and specific examples thereof include ethylene, 1-butene, 3-methyl-1-butene, 1-hexene and 4-methyl-1-pentene.

These? -Olefins may be used singly or in combination of two or more kinds. The random polypropylene may be used singly or in combination of two or more kinds.

Among the random polypropylenes, from the viewpoints of the flexibility, transparency and mechanical strength of the film of the present embodiment, the propylene-ethylene random copolymer, the propylene-1-butene random copolymer, and the propylene- It is more preferable to use at least one selected from the group consisting of

The random polypropylene is a random copolymer of propylene and ethylene or a random copolymer of propylene and an? -Olefin having 4 to 12 carbon atoms in view of flexibility, transparency and balance of characteristics thereof, -Olefin unit content is preferably more than 0.5 mass% and less than 40 mass%, and the content of propylene unit is preferably less than 60 mass% and less than 99.5 mass%.

From the same viewpoint as above, the content of ethylene or? -Olefin unit is more preferably 1% by mass or more but less than 30% by mass, more preferably 1.5% by mass or more and less than 25% by mass, still more preferably 2% More preferable.

The propylene unit content is more preferably 70 mass% or more and less than 99 mass%, still more preferably 75 mass% or more and 98.5 mass% or less, and still more preferably 80 mass% or less and 98 mass% or less.

The content of the propylene unit, the content of the ethylene unit and the content of the? -Olefin unit in the random polypropylene can be measured by a carbon nuclear magnetic resonance (13C-NMR) method.

The melt flow rate (MFR; 230 ° C, according to ISO 1133) of the random polypropylene is preferably 1 to 30 g / 10 min, more preferably 1 to 25 g / 10 min, from the viewpoint of workability and low stickiness of the obtained polypropylene resin composition More preferably 2 to 20 g / 10 min, and still more preferably 3 to 15 g / 10 min.

The catalyst used for producing the random polypropylene is not particularly limited, but for example, a polymerization method using a stereoregular catalyst is preferable.

Examples of the stereoregular catalyst include, but are not limited to, Ziegler catalysts and metallocene catalysts. Of these catalysts, metallocene catalysts are preferred from the viewpoints of transparency, flexibility, and mechanical strength of the film of the present embodiment.

From the viewpoint of transparency, flexibility, and mechanical strength of the film of the present embodiment, the molecular weight distribution (Mw / Mn) of the random polypropylene is preferably 3.5 or less.

Mw / Mn is more preferably 3.0 or less, and still more preferably 2.8 or less.

The lower limit value of Mw / Mn is not particularly limited, but is preferably 1.5 or more. Particularly, it is preferable that the random polypropylene is polymerized by a metallocene catalyst and the molecular weight distribution (Mw / Mn) is 1.5 or more and 3.5 or less. The molecular weight distribution of the random polypropylene is obtained from the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained by GPC measurement.

In the inner layer, the intermediate layer and the outer layer of the film of the present embodiment, other additives may be used in combination depending on the required performance.

Examples of additives include, but are not limited to, flame retardants, stabilizers, coloring agents, pigments, antioxidants, antistatic agents, dispersants, flow enhancers, release agents such as metal stearate, silicone oils, mineral oil- , Antiseptic agents, cross-linking agents, nucleating agents, and the like.

(Composition of film)

As described above, the film of this embodiment has at least an outer layer, an intermediate layer, and an inner layer.

Wherein the outer layer comprises a polypropylene resin, the intermediate layer comprises a polypropylene resin and a hydrogenated block copolymer (a), and the inner layer comprises a polypropylene resin.

The content of the polypropylene resin in the outer layer is preferably 60 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 70 to 100% by mass.

The content of the hydrogenated block copolymer (a) in the outer layer is preferably 0 to 40 mass%, more preferably 0 to 35 mass% , More preferably 0 to 30 mass%.

The content of the polypropylene resin in the intermediate layer is preferably 30 to 90 mass%, more preferably 35 to 85 mass%, and still more preferably 40 to 80 mass%.

The content of the hydrogenated block copolymer (a) in the intermediate layer is preferably 10 to 70 mass%, more preferably 15 to 65 mass%, and still more preferably 20 to 60 mass%.

The content of the polypropylene resin in the inner layer is preferably 50 to 95 mass%, more preferably 55 to 90 mass%, still more preferably 60 to 85 mass%.

The hydrogenated block copolymer (a) may be contained in the inner layer. In this case, the content of the hydrogenated block copolymer (a) in the inner layer is preferably 5 to 50 mass%, more preferably 10 to 45 mass% , And more preferably from 15 to 40 mass%.

By using the above composition, a film having excellent transparency, flexibility, heat sealability, impact resistance, and balance of characteristics thereof can be obtained.

(Preferable Specific Configuration of Inner Layer and Outer Layer)

The film of this embodiment has at least an outer layer, an intermediate layer, and an inner layer,

Wherein said outer layer comprises a polypropylene resin,

Wherein the intermediate layer comprises a polypropylene resin and a hydrogenated block copolymer (a)

Wherein the inner layer comprises a polypropylene resin,

The hydrogenated block copolymer (a)

A polymer block (C) mainly comprising a conjugated diene compound,

A polymer block (B) mainly comprising a conjugated diene compound,

The polymer block (S) containing a vinyl aromatic compound as a main component

Lt; / RTI >

Wherein the content of the polymer block (C) having the conjugated diene compound as a main component in the hydrogenated block copolymer (a) is 1 to 30 mass% and the content of the polymer block (B) containing the conjugated diene compound as the main component is 69 To 98% by mass, the content of the polymer block (S) containing the vinyl aromatic compound as a main component is 1 to 20% by mass,

Wherein the amount of the vinyl block before hydrogenation of the polymer block (C) mainly composed of the conjugated diene compound is 1 to 25 mol%, the amount of vinyl bonds of the polymer block (B) mainly composed of the conjugated diene compound before hydrogenation is 60 to 100 mol% The hydrogenation degree of the hydrogenated block copolymer (a) is 80 mol% or more. Particularly, a configuration described later is preferable.

In a preferred embodiment, the content of the polymer block (C) containing the conjugated diene compound as a main component in the hydrogenated block copolymer (a) is 3 to 13% by mass, and the polymer block (B ) Is 74 to 96 mass%, the content of the polymer block (S) containing the vinyl aromatic compound as a main component is 3 to 13 mass%

The total content of the polymer block (C) containing the conjugated diene compound as a main component and the polymer block (S) containing the vinyl aromatic compound as a main component is 6 to 26% by mass,

And the hydrogenated block copolymer (a) has a hydrogenation rate of 90 mol% or more.

As the film of the present embodiment,

At least an outer layer, an intermediate layer and an inner layer,

Wherein said outer layer comprises a polypropylene resin,

Wherein the intermediate layer comprises a polypropylene resin and a hydrogenated block copolymer (a)

Wherein the inner layer comprises a polypropylene resin,

Wherein the content of the vinyl aromatic compound monomer unit in the hydrogenated block copolymer (a) is 3 to 13 mass%

Wherein the hydrogenation block copolymer (a) has a hydrogenation rate of 90 mol%

The amount of butylene and / or propylene in the hydrogenated block copolymer (a) is 60 to 85 mol% based on 100 mol% of the total of the conjugated diene compound units,

The hydrogenated block copolymer (a) has a peak of crystallization at 0 to 60 캜,

Wherein the hydrogenated block copolymer (a) has a crystallization calorie of 1.0 to 8.0 J / g,

Wherein the hydrogenated block copolymer (a) has a Shore A hardness of 25 to 55,

Film.

The film of the present embodiment may be a film in which the outer layer, the intermediate layer, and the inner layer are made the same and the intermediate layer is laminated in three layers.

<First Configuration>

The film of the present embodiment is characterized in that the outer layer comprises the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the block copolymer (b1) is a polymer block mainly composed of the conjugated diene compound (C) is not included,

Wherein the hydrogenated block copolymer (b1) comprises a polymer block (B1) composed mainly of a conjugated diene compound and a polymer block (S1) composed mainly of a vinyl aromatic compound,

Wherein the content of the polymer block (B1) having the conjugated diene compound as a main component in the hydrogenated block copolymer (b1) is 75 to 92 mass%, the content of the polymer block (S1) containing the vinyl aromatic compound as the main component is 8 To 25% by mass,

Wherein the hydrogenated block copolymer (b1) has a hydrogenation degree of not less than 80 mol%, and the hydrogenated block copolymer (b1) has a hydrogenation amount of not less than 40 mol%

The content of the polypropylene resin in the outer layer is 60 to 100 mass%

It is preferable that the content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the outer layer is 0 to 40% by mass.

By having the above-mentioned constitution, a film excellent in transparency, flexibility, and balance of characteristics thereof can be obtained.

With regard to the hydrogenated block copolymer (b1), the hydrogenated block copolymer (a) as well as the hydrogenated block copolymer (a) and the hydrogenated block copolymer And can be controlled as well.

&Lt; Second Configuration >

The film of the present embodiment is characterized in that the inner layer contains the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the block copolymer (b1) is a polymer block mainly composed of the conjugated diene compound (C) is not included,

Wherein the hydrogenated block copolymer (b1) comprises a polymer block (B1) composed mainly of a conjugated diene compound and a polymer block (S1) composed mainly of a vinyl aromatic compound,

Wherein the content of the polymer block (B1) having the conjugated diene compound as a main component in the hydrogenated block copolymer (b1) is 75 to 92 mass%, the content of the polymer block (S1) containing the vinyl aromatic compound as the main component is 8 To 25% by mass,

Wherein the hydrogenated block copolymer (b1) has a hydrogenation degree of not less than 80 mol%, and the hydrogenated block copolymer (b1) has a hydrogenation amount of not less than 40 mol%

The content of the polypropylene resin in the inner layer is 50 to 96 mass%

The content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the inner layer is preferably 5 to 50 mass%.

By having the above-mentioned constitution, a film excellent in transparency, flexibility, and balance of characteristics thereof can be obtained.

With regard to the hydrogenated block copolymer (b1), the hydrogenated block copolymer (a) is preferably used as the "main component", the respective materials of the conjugated diene compound and the vinyl aromatic compound, the amount of vinyl bonding, And can be controlled as well.

&Lt; Third Configuration >

The film of the present embodiment is characterized in that the outer layer further comprises a hydrogenated block copolymer (b2)

Wherein the hydrogenated block copolymer (b2) comprises a polymer block (B2) composed mainly of a conjugated diene compound and a polymer block (S2) composed mainly of a vinyl aromatic compound,

Wherein the content of the polymer block (B2) mainly composed of the conjugated diene compound in the hydrogenated block copolymer (b2) is 75 to 92 mass% and the content of the polymer block (S2) composed mainly of the vinyl aromatic compound is 8 To 25% by mass,

Wherein the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%, and the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%

The hydrogenated block copolymer (b2)

Wherein the polymer contains two or more polymer blocks (B2) containing the conjugated diene compound as a main component,

It is preferable that the content of the polymer block (B-2) present at the end of the hydrogenated block copolymer (b2) in the hydrogenated block copolymer is 1 to 10% by mass in the polymer block (B2) containing the conjugated diene compound as a main component desirable.

&Lt; Fourth Configuration >

The film of the present embodiment is characterized in that the inner layer further comprises a hydrogenated block copolymer (b2)

Wherein the hydrogenated block copolymer (b2) comprises a polymer block (B2) composed mainly of a conjugated diene compound and a polymer block (S2) composed mainly of a vinyl aromatic compound,

Wherein the content of the polymer block (B2) mainly composed of the conjugated diene compound in the hydrogenated block copolymer (b2) is 75 to 92 mass% and the content of the polymer block (S2) composed mainly of the vinyl aromatic compound is 8 To 25% by mass,

Wherein the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%, and the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%

The hydrogenated block copolymer (b2)

Wherein the polymer contains two or more polymer blocks (B2) containing the conjugated diene compound as a main component,

It is preferable that the content of the polymer block (B-2) present at the end of the hydrogenated block copolymer (b2) in the hydrogenated block copolymer is 1 to 10% by mass in the polymer block (B2) containing the conjugated diene compound as a main component desirable.

The hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) and / or the hydrogenated block copolymer (b1) in the outer layer have a polypropylene resin content of 60 to 100 mass% The content of the copolymer (b2) is preferably 0 to 40% by mass.

The hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) and / or the hydrogenated block copolymer (b1) in the inner layer may be used in an amount of 50 to 95 mass% Or the hydrogenated block copolymer (b2) is 5 to 50% by mass.

By having the above-described constitution, a film excellent in transparency, flexibility, heat sealability, impact resistance and balance of characteristics thereof can be obtained.

The content of the polymer block (B-2) present at the end of the hydrogenated block copolymer (b2) can be controlled by the amount of the conjugated diene compound added.

The content of the polymer block (B-2) present at the end of the hydrogenated block copolymer (b2) is preferably 2 to 8% by mass, more preferably 2 to 6% by mass in the hydrogenated block copolymer (b2) More preferable.

(Method for producing hydrogenated block copolymer (b1) and hydrogenated block copolymer (b2)) [

The hydrogenated block copolymer (b1) and the hydrogenated block copolymer (b2) can be produced by the same method as in the above-mentioned hydrogenated block copolymer (a).

(Structural Example of Hydrogenated Block Copolymer (b1)) [

The above-mentioned hydrogenated block copolymer (b1) includes, for example, those having a structure represented by the following general formula.

(S1-B1) _n ,

S1- (B1-S1) _n ,

B1- (S1-B1) _n ,

[(B1-S1) _n ] _m -Z,

[(S1-B1) _n ] _m -Z,

[(B 1 -S 1) _n -B 1] _m -Z,

[(S1-B1) _n -S1] _m- Z

In the above general formula, S1 is a polymer block (S1) having a vinyl aromatic compound monomer unit as a main component, and B1 is a polymer block (B1) having a conjugated diene compound monomer unit as a main component.

The boundary line between the polymer block (S1) and the polymer block (B1) need not be clearly distinguished.

Also, n is an integer of 1 or more, preferably an integer of 1 to 5.

m is an integer of 2 or more, preferably 2 to 11, more preferably 2 to 8.

Z represents a coupling agent residue. Here, the term "coupling residue" means that a plurality of copolymers of a conjugated diene compound monomer unit and a vinyl aromatic hydrocarbon monomer unit are provided between the polymer block (S1) and the polymer block (S1), the polymer block (B1) Means a residue after coupling of a coupling agent used for bonding in the liver, or between the polymer block (S1) and the polymer block (B1).

Examples of the coupling agent include bifunctional coupling agents and polyfunctional coupling agents. Examples of the bifunctional coupling agent include, but are not limited to, dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; And acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate and phthalic acid esters.

The polyfunctional coupling agent having three or more functional groups is not limited to the following examples, and examples thereof include polyvalent epoxy compounds such as trivalent or higher polyalcohols, epoxidized soybean oil, and diglycidyl bisphenol A; A halogenated silicon compound represented by the formula R ¹ _(4-n) SiX _n (wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is halogen and n is an integer of 3 or 4) .

Examples of the halogenated silicon compound include, but are not limited to, methyl silyl trichloride, t-butyl silyl trichloride, silicon tetrachloride, and bromides thereof.

Examples of the halogenated tin compound include, but are not limited to, polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Further, dimethyl carbonate, diethyl carbonate and the like can also be used.

In the above general formulas, the vinyl aromatic compound monomer units in the polymer block (S1) and the polymer block (B1) may be uniformly distributed or distributed in a tapered form. When the polymer block (S1) and the polymer block (B1) are a copolymer block of a vinyl aromatic monomer unit and a conjugated diene compound monomer unit, the vinyl aromatic monomer unit in the copolymer block has a uniform distribution And / or a plurality of tapered portions may be present. In the copolymer block portion, a plurality of portions having different contents of vinyl aromatic compound monomer units may coexist.

(Structural Example of Hydrogenated Block Copolymer (b2)) [

As the hydrogenated block copolymer (b2), for example, those having a structure represented by the following general formula can be cited.

(S2-B2) _n ,

B2- (S2-B2) _n ,

[(B2-S2) _n ] _m -Z,

[(B2-S2) _n- B2] _m- Z,

In the above general formula, S2 is a polymer block (S2) having a vinyl aromatic compound monomer unit as a main component and B2 is a polymer block (B2) having a conjugated diene compound monomer unit as a main component.

The boundary line between the polymer block (S2) and the polymer block (B2) need not be clearly distinguished.

Also, n is an integer of 1 or more, preferably an integer of 1 to 5.

m is an integer of 2 or more, preferably 2 to 11, more preferably 2 to 8.

Z represents a coupling agent residue.

Here, the coupling residue means a polymer block (S2) - a polymer block (S2), a polymer block (B2) - a polymer block (B2), and a polymer block Means a residue after coupling of a coupling agent used for bonding between the polymer and the polymer block (S2) - the polymer block (B2).

Examples of the coupling agent include bifunctional coupling agents and polyfunctional coupling agents.

Examples of the bifunctional coupling agent include, but are not limited to, dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; And acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate and phthalic acid esters.

The polyfunctional coupling agent having three or more functional groups is not limited to the following examples, and examples thereof include polyvalent epoxy compounds such as trivalent or higher polyalcohols, epoxidized soybean oil, and diglycidyl bisphenol A; A halogenated silicon compound represented by the formula R ¹ _(4-n) SiX _n (wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is halogen and n is an integer of 3 or 4) .

Examples of the halogenated silicon compound include, but are not limited to, methyl silyl trichloride, t-butyl silyl trichloride, silicon tetrachloride, and bromides thereof.

Examples of the halogenated tin compound include, but are not limited to, polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Further, dimethyl carbonate, diethyl carbonate and the like can also be used.

In the above general formulas, the vinyl aromatic compound monomer units in the polymer block (S2) and the polymer block (B2) may be uniformly distributed or may be distributed in a tapered form. When the polymer block (S2) and the polymer block (B2) are a copolymer block of a vinyl aromatic monomer unit and a conjugated diene compound monomer unit, the vinyl aromatic monomer unit in the copolymer block is uniformly distributed And / or a plurality of tapered portions may be present. In the copolymer block portion, a plurality of portions having different contents of vinyl aromatic compound monomer units may coexist.

As the hydrogenated block copolymer (b2), a structure represented by the following general formula is particularly preferable.

That is, a polymer block (B-2) is present at the end of the hydrogenated block copolymer (b2) in the polymer block (B2) having a conjugated diene compound as a main component.

S2-B2-S2- (B-2)

S2 - (B2 - S2) _n - (B-2)

(B-2) -S2- (B2-S2) _n - (B-2)

The above-mentioned hydrogenated block copolymer (b2) is included in the concept of the hydrogenated block copolymer (b1) and has a preferable structure among the hydrogenated block copolymers (b1) from the viewpoint of the film characteristics of the present embodiment .

In the film of the present embodiment, both the hydrogenated block copolymer (b1) and the hydrogenated block copolymer (b2) are included in the outer layer and / or the inner layer. In this case, , The production amount of the hydrogenated block copolymer (b2) having the constituent requirements of the hydrogenated block copolymer (b2) and the production amount of the hydrogenated block copolymer (b1) without the constituent requirements of the hydrogenated block copolymer (b2) The content of the hydrogenated block copolymer (b2) and the hydrogenated block copolymer (b1) in the outer layer and / or inner layer can be determined by confirming the addition amount or the addition method of the monomers.

(A method for producing a material constituting each layer of a film)

The resin material constituting each layer of the film of the present embodiment can be obtained, for example, from a hydrogenated block copolymer (a), a polypropylene resin, a hydrogenated block copolymer (b1), a hydrogenated block copolymer (b2) Therefore, it can be produced by appropriately selecting other components to be added, by a method of dry-blending them, or by a method of adjusting by a device provided for mixing of a common polymer material.

The mixing device is not particularly limited, and examples thereof include a Banbury mixer, a kneader, a Labo plastometer, a single screw extruder, a twin screw extruder, and the like, and the melt mixing method using an extruder is effective for productivity , And good kneadability.

The melting temperature at the time of kneading can be appropriately set, but it is usually in the range of 130 to 300 占 폚, preferably in the range of 150 to 250 占 폚.

(Film Forming Method)

The method of producing the film of the present embodiment is not particularly limited. For example, a T-die method, an inflation method, or the like can be employed as a molding method in which a polypropylene resin composition is put in an extruder and extruded.

As the inflation molding, ordinary air-cooled inflation molding, air-cooled two-stage inflation molding, high-speed inflation molding, water-cooled inflation molding and the like can be employed.

Further, a blow molding method such as direct blowing or injection blowing, or a press molding method may be employed.

As the extruder to be used, a single or multi-screw extruder may be used, or a multilayer film extruded by using a plurality of extruders may be molded.

In addition, the polypropylene resin composition may be directly molded from an extruder as a film.

The film of the present embodiment is excellent in transparency, flexibility, and balance of characteristics thereof, as shown in Examples described later.

Taking the above characteristics into consideration, the film of the present embodiment can be applied to a variety of medical (clothing) type packaging, various food packaging, household goods packaging, industrial material packaging, various rubber products, resin products, leather products, Sheet products such as food and beverage packs, frozen food containers, television sets, stereos, vacuum cleaners, etc., for example, industrial products such as stretch tape and dicing film used, protective films used for protecting construction materials and steel plates, substrates for adhesive films, Waterproofing, waterproof sheets, civil engineering packing, daily necessities, leisure articles, toys, industrial articles, furniture articles, writing utensils, etc. for use in automobile interior and exterior parts such as bumper parts, body panels and side seals, A transparent pocket, a holder, a cover such as a file, and a medical bag such as a sap bag.

In particular, it can be preferably used as a film for medical treatment and a packaging material such as a food packaging material and a medical (packaging) material.

Example

Hereinafter, the present embodiment will be described in detail by way of examples, but the present embodiment is not limited to these examples.

In Examples and Comparative Examples, a hydrogenated block copolymer was produced by the method described below to prepare a film, and the physical properties thereof were compared.

At that time, the properties of the hydrogenated block copolymer and the physical properties of the film were measured as follows.

[Evaluation method of hydrogenated block copolymer]

(1) Content of all vinyl aromatic compound units (hereinafter also referred to as &quot; styrene content &quot;)

The content of all the vinyl aromatic monomer units in the hydrogenated block copolymer was measured by proton nuclear magnetic resonance ( ¹ H-NMR) method using the hydrogenated block copolymer after hydrogenation.

The measurement was conducted using JNM-LA400 (manufactured by JEOL), deuterated chloroform as a solvent, a sample concentration of 50 mg / mL, an observation frequency of 400 MHz, tetramethylsilane as a chemical shift standard, a pulse delay of 2.904 seconds, 64 times, a pulse width of 45 degrees and a measurement temperature of 26 占 폚.

The styrene content was calculated by using the integrated value of total styrene aromatic signals at 6.2 to 7.5 ppm of the spectrum.

(2) Amount of vinyl bond before hydrogenation

The amount of vinyl bond before hydrogenation was measured by a proton nuclear magnetic resonance ( ¹ H-NMR) method, and the amount of vinyl bond before hydrogenation of the polymer block was obtained by measuring the polymer sampled every step of the block copolymer polymerization process before hydrogenation.

The measurement conditions and measurement data were processed in the same manner as in (1) above.

The amount of vinyl bonding is calculated by calculating the integral value per 1 H of each bonding mode from the integral value of 1,4-bond and 1,2-bond attributed to 1,4-bond and 1,2-bond, Lt; / RTI &gt;

(3) Hydrogenation rate

The hydrogenation ratio of the hydrogenated block copolymer was measured by proton nuclear magnetic resonance ( ¹ H-NMR) using the hydrogenated block copolymer after hydrogenation.

The measurement conditions and the method of processing the measurement data were the same as in the above (1).

The hydrogenation rate was obtained by calculating the integral value of the signal derived from the residual double bond of 4.5 to 5.5 ppm and the signal derived from the hydrogenated conjugated diene, and calculating the ratio.

(4) Measurement of number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrogenated block copolymer were measured by gel permeation chromatography (GPC) (Shimadzu Corporation, LC-10), column: TSKgelGMHXL (4.6 mm ID x 30 cm, , And the solvent: tetrahydrofuran (THF), the polystyrene reduced molecular weight by a commercially available standard polystyrene.

The molecular weight distribution of the hydrogenated block copolymer was obtained as the ratio (Mw) / (Mn) of the obtained number average molecular weight (Mn) to weight average molecular weight (Mw).

(5) the amount of butylene and / or the amount of propylene relative to the total 100 mol% of the conjugated diene compound units

The hydrogenated block copolymer after hydrogenation was measured by proton nuclear magnetic resonance ( ¹ H-NMR).

The measurement conditions and the measurement data were processed in the same manner as in the above (2) and (3).

The butylene content was calculated by calculating the integral value of the signal attributed to butylene (hydrogenated 1,2-linkage) and propylene (hydrogenated 3,4-linkage) at 0 to 2.0 ppm of the spectrum, Respectively.

(6) DSC measurement

10 mg of the hydrogenated block copolymer was respectively quenched in an aluminum pan and subjected to an initial temperature of -50 占 폚 in a nitrogen atmosphere (flow rate: 50 ml / min) using a differential scanning calorimeter (DSC) (Q2000 manufactured by TA Instruments Co., Ltd.) , The temperature was raised to 150 占 폚 at a heating rate of 10 占 폚 / min, held at 150 占 폚 for 5 minutes, and then lowered to -50 占 폚 at 10 占 폚 / min.

The crystallization peak appearing in the descending process of the drawn DSC curve is referred to as the crystallization temperature (占 폚), and the heat quantity represented by the crystallization peak area is defined as the crystallization heat quantity (J / g).

(7) Shore A hardness of hydrogenated block copolymer

The hydrogenated block copolymer had a Shore A hardness (according to ASTM D-2240) of four compression-molded sheets of 2 mm in thickness, and the instantaneous value was measured with a durometer type A.

[Method for evaluating characteristics of film]

(1) Tensile modulus

The film was punched with a JIS No. 5 test piece to obtain a measurement sample. The measurement sample was measured at a tensile rate of 200 mm / min in accordance with JIS K7127 in the flow direction (MD direction) of the resin for the measurement sample.

The tensile elastic modulus was calculated from the respective stresses corresponding to the strains of 0.05% and 0.25%, and it was determined as an index of flexibility. The obtained tensile modulus was evaluated according to the following criteria.

?: Tensile modulus less than 400 MPa

?: Tensile modulus of elasticity of 400 MPa or more and less than 500 MPa

DELTA: tensile modulus of elasticity of not less than 500 MPa and less than 600 MPa

X: tensile modulus of elasticity of 600 MPa or more

(2) Hayes

The haze of the film was measured using a haze meter (NDH-1001DP, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the haze was measured and used as an index of transparency. From the obtained haze value, the following criteria were used.

○: Haze value is less than 15

DELTA: haze value of not less than 15 and less than 20

X: haze value of 20 or more

(3) Heat sealability

Two sheets of the film were superimposed and heat-sealed by using a heat sealer (TP-701-B, manufactured by Tester Corporation) under the conditions of a seal temperature of 160 캜, a seal time of 5 seconds and an actual pressure of 0.2 MPa, A sample was obtained.

After the obtained sample was allowed to stand at 23 占 폚 for 24 hours or more, a test piece having a width of 15 mm was cut out in a direction perpendicular to the seal width direction to obtain a test piece having a seal portion of 10 mm 占 15 mm.

Subsequently, the seal portion of the test piece was peeled 180 ° at a rate of 200 mm / min by a tensile tester (Minneve, TGE-500N), and the heat seal strength (N / 15 mm) per 15 mm width was measured. Respectively.

From the obtained heat seal strength, evaluation was made according to the following criteria.

?: Heat seal strength at a heat seal temperature of 160 占 폚 of 25 N / 15 mm or more

?: Heat seal strength at a heat seal temperature of 160 占 폚 is 15N / 15mm or more and less than 25N / 15mm

?: Heat seal strength at a heat seal temperature of 160 占 폚 is 10N / 15mm or more and less than 15N / 15mm

X: Heat seal strength at a heat seal temperature of 160 캜 is less than 10 N / 15 mm

(4) Vapor permeability

And the water vapor permeability was measured by a water vapor permeability meter (type L80-5000, manufactured by Lyssy) according to JIS K 7129 A method (humidity sensor method).

The water vapor permeability of Comparative Example 4 was assumed to be 100, which is a reference value.

(Water vapor permeability of Examples and Comparative Examples) / (water vapor permeability of Comparative Example 4) x 100

The smaller the value of the water vapor permeability, the better the water vapor barrier property.

[Evaluation method of medical container]

(5) Impact resistance of medical container

The film was cut out with a test piece of 20 cm x 13 cm, and two test pieces were superimposed. The three sides were heat-sealed at 145 캜 for 2 seconds to prepare a bag.

500 mL of water was placed in the bag, and the remaining one side was heat-sealed under the same conditions to prepare a bag containing water.

The bag containing the water was sterilized by steam, and then allowed to stand in a refrigerated room at 4 캜 for 24 hours. Thereafter, 10 bags were dropped from a height of 1.8 m, and the bag rupture rate And measured as an index of impact resistance.

From the obtained wave ratio, the following criteria were used.

?: The non-breakage ratio is 100%

○: Non-peaking ratio is 70% or more and less than 100%

?: Peak ratio of 50% or more and less than 70%

X: Less than 50%

(6) CFC measurement of a molded article on a film

The elution temperature-elution amount curve by the temperature-rising elution fraction was measured as follows, using the molded body obtained in the examples and comparative examples in Tables 2 and 3 as test samples, and the elution amount at each temperature, The molecular weight distribution of the component was determined.

First, the column containing the filler was heated to 145 占 폚, and the sample solution in which the hydrogenated block copolymer composition was dissolved in orthodichlorobenzene was introduced and held at 140 占 폚 for 30 minutes. Then, the temperature of the column was lowered to -20 占 폚 at a cooling rate of 1 占 폚 / min, and then held for 60 minutes to deposit a sample on the surface of the filler.

Thereafter, the temperature of the column was gradually raised at a heating rate of 40 占 폚 / minute and at an interval of 5 占 폚, and the concentration of the eluted sample at each temperature was detected. Then, the elution temperature-elution amount curve was measured from the elution amount (mass%) of the sample and the value of the column internal temperature (占 폚) at that time, and the elution amount and the molecular weight distribution at each temperature were determined.

Apparatus: CFC type cross-fractionation chromatograph (manufactured by Polymer Char)

Detector: IR type infrared spectrophotometer (manufactured by Polymer Char)

Detection wavelength: 3.42 탆

Column: Shodex HT-806M x 3 (manufactured by Showa Denko Co., Ltd.)

Column Calibration: Monodisperse polystyrene (manufactured by TOSOH CORPORATION)

· Molecular weight calibration method: nominal calibration method (in terms of polystyrene)

Eluent: Orthodichlorobenzene

· Flow rate: 1.0 mL / min

Sample concentration: 120 mg / 30 mL

· Injection amount: 0.5 mL

From the obtained elution temperature-elution amount curve, an integrated elution amount (%) in a total capacity of -20 占 폚 or less, an integrated elution amount (%) in a total capacity in a range exceeding -20 占 폚 and less than 60 占 폚, The integral elution amount (%) in the total capacity and the molecular weight distribution of the elution component at 10 to 60 캜 were obtained.

[Process for producing hydrogenated block copolymer (a)]

(Preparation of hydrogenation catalyst)

The hydrogenation catalyst used in the hydrogenation reaction of the hydrogenated block copolymer was prepared by the following method.

To the reaction vessel purged with nitrogen, 1 liter of dried and purified cyclohexane was added, 100 millimoles of bis (eta 5-cyclopentadienyl) titanium dichloride was added, and a n-hexane solution containing 200 millimoles of trimethylaluminum And the mixture was reacted at room temperature for about 3 days.

(Production of hydrogenated block copolymer (a-1)) [

Batch polymerization was carried out using an internal 10 L stirring apparatus and jacket-equipped molding reactor.

1 liter of cyclohexane was charged into the reactor and then 0.050 parts by mass of n-butyllithium (hereinafter also referred to as "Bu-Li") was added to 100 parts by mass of the entire monomer, and N, N, N ' N'-tetramethylethylenediamine (hereinafter also referred to as "TMEDA") was added in an amount of 0.05 mol per 1 mol of Bu-Li.

As a first step, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of butadiene was added over 10 minutes, and then further polymerized for 10 minutes. During the polymerization, the temperature was controlled at 65 占 폚.

Next, as a second step, 1.50 moles of TMEDA with respect to 1 mole of Bu-Li and 0.05 mole of sodium t-pentoxide (hereinafter referred to as NaOAm) relative to 1 mole of Bu-Li were added, and 85 parts by mass of butadiene (Concentration: 20% by mass) was added over a period of 60 minutes, and then further polymerized for 10 minutes. During the polymerization, the temperature was controlled at 60 占 폚.

Next, as a third step, a cyclohexane solution (concentration 20% by mass) containing 5 parts by mass of styrene was added over 5 minutes, and then further polymerized for 10 minutes. During the polymerization, the temperature was controlled at 65 占 폚.

Further, the polymer was sampled at every step obtained in the process of adjusting the block copolymer. The obtained block copolymer had an analysis value of a styrene content of 5 mass%, a weight average molecular weight of 249,000, and a molecular weight distribution of 1.12.

Subsequently, the hydrogenation catalyst was added to the obtained block copolymer in an amount of 100 ppm as titanium per 100 parts by mass of the block copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 占 폚.

Thereafter, methanol was added, and then 0.3 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to the block copolymer.

The obtained hydrogenated block copolymer (a-1) had a hydrogenation rate of 99.5% and an MFR of 2 g / 10 min.

The results of the analysis of the obtained hydrogenated block copolymer (a-1) are shown in Table 1.

(Preparation of hydrogenated block copolymer (a-2)) [

The fourth step is added as the first step and 10 parts by mass of butadiene are used as the second step and 82 parts by mass of butadiene are used as the third step and 5 parts by mass of styrene, Cyclohexane solution (concentration: 20% by mass) containing 3 parts by mass of propylene carbonate was added over 5 minutes, and then further polymerized for 10 minutes. The hydrogenated block copolymer (a-2) was prepared by conducting the same operation as the hydrogenated block copolymer (a-1) except that the temperature was controlled to 65 캜 during the polymerization and the block copolymer was prepared .

The obtained hydrogenated block copolymer (a-2) had a styrene content of 5 mass%, a weight average molecular weight of 251,000, a molecular weight distribution of 1.14, a hydrogenation rate of 99.8%, and an MFR of 4 g / 10 min. The results of the analysis of the obtained hydrogenated block copolymer (a-2) are shown in Table 1.

(Preparation of hydrogenated block copolymer (a-3)) [

Except that Bu-Li was changed to 0.060 parts by mass, and 15 parts by mass of butadiene was used as the first step, 78 parts by mass of butadiene was used as the second step, and 7 parts by mass of styrene was used as the third step. , And the same operation as in the above-mentioned hydrogenated block copolymer (a-1) was carried out to prepare a hydrogenated block copolymer (a-3).

The obtained hydrogenated block copolymer (a-3) had a styrene content of 7 mass%, a weight average molecular weight of 204,000, a molecular weight distribution of 1.19, a hydrogenation rate of 99.6%, and an MFR of 2.9 g / 10 min.

The results of the analysis of the obtained hydrogenated block copolymer (a-3) are shown in Table 1.

(Preparation of hydrogenated block copolymer (a-4)) [

Except that 0.053 mass parts of Bu-Li was used as the first step, 3 mass parts of butadiene was used as the second step, 85 mass parts of butadiene was used as the second step, and 12 mass parts of styrene was used as the third step. The hydrogenated block copolymer (a-1) was subjected to the same operation as the above-mentioned hydrogenated block copolymer block copolymer (a-1) to prepare a hydrogenated block copolymer (a-4).

The obtained hydrogenated block copolymer (a-4) had a styrene content of 12 mass%, a weight average molecular weight of 225,000, a molecular weight distribution of 1.22, a hydrogenation rate of 99.3%, and an MFR of 1.9 g / 10 min.

The results of the analysis of the obtained hydrogenated block copolymer (a-4) are shown in Table 1.

(Preparation of hydrogenated block copolymer (a-5)) [

Except that the block copolymer was prepared by making Bu-Li as 0.042 parts by mass, butadiene as 6 parts by mass as the first step, 93 parts by mass of butadiene as the second step, and 3 parts by mass of styrene as the third step, The same operation as in the above-mentioned hydrogenated block copolymer (a-1) was carried out to prepare a hydrogenated block copolymer (a-5).

The obtained hydrogenated block copolymer (a-5) had a styrene content of 3 mass%, a weight average molecular weight of 282,000, a molecular weight distribution of 1.29, a hydrogenation ratio of 98.6%, and an MFR of 3.9 g / 10 min.

The results of the analysis of the obtained hydrogenated block copolymer (a-5) are shown in Table 1.

(Preparation of hydrogenated block copolymer (a-6)) [

Except that the block copolymer was prepared by using Bu-Li as 0.078 parts by mass, butadiene as 16 parts by mass as the first step, 72 parts by mass of butadiene as the second step, and 12 parts by mass of styrene as the third step, The hydrogenated block copolymer (a-1) was subjected to the same operation as in the above-mentioned hydrogenated block copolymer (a-6).

The obtained hydrogenated block copolymer (a-6) had a styrene content of 12 mass%, a weight average molecular weight of 161,000, a molecular weight distribution of 1.12, a hydrogenation rate of 99.0%, and an MFR of 1.5 g / 10 min.

The results of the analysis of the obtained hydrogenated block copolymer (a-6) are shown in Table 1.

(Production of hydrogenated block copolymer (a-7)) [

Except that the block copolymer was prepared by using Bu-Li as 0.099 parts by mass, butadiene as 17 parts by mass as the first step, 67 parts by mass of butadiene as the second step, and 16 parts by mass of styrene as the third step, The hydrogenated block copolymer (a-1) was subjected to the same operation as in the above-mentioned hydrogenated block copolymer (a-7).

The obtained hydrogenated block copolymer (a-7) had a styrene content of 16 mass%, a weight average molecular weight of 117,000, a molecular weight distribution of 1.09, a hydrogenation rate of 99.2%, and an MFR of 1.8 g / 10 min.

The results of the analysis of the obtained hydrogenated block copolymer (a-7) are shown in Table 1.

(Production of hydrogenated block copolymer (a-8)) [

Mentioned hydrogenated block copolymer (a-1) was produced in the same manner as in Example 1 except that 0.015 parts by mass of Bu-Li was used as the first step, 20 parts by mass of butadiene was used as the first step, and 80 parts by mass of butadiene was used as the second step. Was carried out in the same manner as in Example 1 to prepare a hydrogenated block copolymer (a-8).

The obtained hydrogenated block copolymer (a-8) had a styrene content of 0% by mass, a weight average molecular weight of 250,000, a molecular weight distribution of 1.08, a hydrogenation rate of 99.5% and an MFR of 32 g / 10 minutes.

The results of the analysis of the obtained hydrogenated block copolymer (a-8) are shown in Table 1.

(Production of hydrogenated block copolymer (a-9)) [

Except that 0.1 part by mass of Bu-Li was used as the first step, 5 parts by mass of butadiene was used as the second step, 70 parts by mass of butadiene was used as the second step, and 25 parts by mass of styrene was used as the third step. The same operation as in the above-mentioned hydrogenated block copolymer (a-1) was carried out to prepare a hydrogenated block copolymer (a-9).

The obtained hydrogenated block copolymer (a-9) had a styrene content of 25 mass%, a weight average molecular weight of 88,000, a molecular weight distribution of 1.11, a hydrogenation rate of 99.0%, and an MFR of 3.1 g / 10 min.

The results of the analysis of the obtained hydrogenated block copolymer (a-9) are shown in Table 1.

(Preparation of hydrogenated block copolymer (a-10)) [

Except that the block copolymer was prepared by making Bu-Li as 0.072 parts by mass and by using 35 parts by mass of butadiene as the first step and 63 parts by mass of butadiene as the second step and 2 parts by mass of styrene as the third step, The same operation as in the above-mentioned hydrogenated block copolymer (a-1) was carried out to prepare a hydrogenated block copolymer (a-10).

The obtained hydrogenated block copolymer (a-10) had a styrene content of 2% by mass, a weight average molecular weight of 169,000, a molecular weight distribution of 1.12, a hydrogenation rate of 98.3%, and an MFR of 4.8 g / 10 minutes.

The results of the analysis of the obtained hydrogenated block copolymer (a-10) are shown in Table 1.

(Preparation of hydrogenated block copolymer (a-11)) [

The first step is to 10 parts by mass of butadiene, the second step is to 85 parts by mass of butadiene, and the third step is performed with 5 parts by mass of styrene The hydrogenated block copolymer (a-11) was produced in the same manner as in the hydrogenated block copolymer (a-1) except that the block copolymer was prepared.

The obtained hydrogenated block copolymer (a-11) had a styrene content of 5% by mass, a weight average molecular weight of 248,000, a molecular weight distribution of 1.16, a hydrogenation rate of 99.1%, and an MFR of 9.2 g / 10 minutes.

The results of the analysis of the obtained hydrogenated block copolymer (a-11) are shown in Table 1.

(Production of hydrogenated block copolymer (a-12)

The hydrogenated block copolymer (a-1) was subjected to the same operation as described above to polymerize the block copolymer, and then the hydrogenated block copolymer (a-13) whose hydrogenation rate was controlled was prepared.

The obtained hydrogenated block copolymer (a-13) had a styrene content of 5% by mass, a weight average molecular weight of 253,000, a molecular weight distribution of 1.15, a hydrogenation ratio of 70.0% and an MFR of 15.2 g / 10 minutes.

The results of the analysis of the obtained hydrogenated block copolymer (a-12) are shown in Table 1.

(Production of hydrogenated block copolymer (a-13)

The same operation as in the hydrogenated block copolymer (a-1) was carried out except that the Bu-Li was changed to 0.055 parts by mass, the TMEDA before the second step was changed to 0.65 mol, and the block copolymer was prepared without adding NaOAm. To thereby prepare a block copolymer (a-14).

The obtained hydrogenated block copolymer (a-14) had a styrene content of 5% by mass, a weight average molecular weight of 239,000, a molecular weight distribution of 1.08, a hydrogenation rate of 99.4%, and an MFR of 2.9 g / 10 minutes.

The results of the analysis of the obtained hydrogenated block copolymer (a-14) are shown in Table 1.

The results of the analysis of the hydrogenated block copolymers (a-1) to (a-13) obtained as described above are shown in Table 1.

[Process for producing hydrogenated block copolymer ((b1): b1-1 to b1-3)]

(Hydrogenated block copolymer (b1-1))

Batch polymerization was carried out by using a stirrer having a volume of 10 L and a jacketed reactor. First, 1 L of cyclohexane was charged, and then 0.065 parts by mass of n-butyllithium (hereinafter, referred to as Bu-Li) with respect to 100 parts by mass of the total monomer was mixed with N, N, N ' 0.05 mol of diamine (hereinafter referred to as TMEDA) per mole of Bu-Li and 0.05 mol of sodium t-pentoxide (hereinafter referred to as NaOAm) per 1 mol of Bu-Li were added.

As a first step, a cyclohexane solution (concentration 20 mass%) containing 8 parts by mass of styrene was added over 5 minutes, and then further polymerized for 5 minutes. During the polymerization, the temperature was controlled at 60 占 폚.

Next, as a second step, a cyclohexane solution (concentration 20% by mass) containing 85 parts by mass of butadiene was added over 60 minutes and then further polymerized for 5 minutes. During the polymerization, the temperature was controlled at 55 占 폚.

Next, as a third step, a cyclohexane solution (concentration 20% by mass) containing 7 parts by mass of styrene was added over 5 minutes and then further polymerized for 5 minutes. During the polymerization, the temperature was controlled at 60 占 폚.

The obtained block copolymer had a styrene content of 15% by mass, a butadiene block portion having a vinyl bond content of 78% before hydrogenation, a weight average molecular weight of 178,000, and a molecular weight distribution of 1.12.

Subsequently, the hydrogenation catalyst was added to the obtained block copolymer in an amount of 100 ppm as titanium per 100 parts by mass of the block copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 占 폚.

Then, methanol was added, and then 0.3 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to the block copolymer.

The obtained hydrogenated block copolymer (b1-1) had a hydrogenation rate of 99.2% and an MFR of 4.8 g / 10 min.

The results of the analysis of the resulting hydrogenated block copolymer (b1-1) are shown in Table 1.

(Hydrogenated block copolymer (b1-2))

As the first step, 12 mass parts of styrene was added over 10 minutes, and then further polymerization was carried out for 5 minutes, with Bu-Li being 0.095 mass parts relative to 100 mass parts of the whole monomers. During the polymerization, the temperature was controlled at 60 占 폚.

Next, as a second step, 88 parts by mass of butadiene was added over 60 minutes, and then further polymerized for 5 minutes. During the polymerization, the temperature was controlled at 55 占 폚. Next, dimethyldimethoxysilane was added in an amount of 0.25 mol based on 1 mol of Bu-Li to perform a coupling reaction. Thereafter, the mixture was stirred at 60 占 폚 for 10 minutes to carry out the same operation as the hydrogenated block copolymer (b1-1) except that a block copolymer was prepared to prepare a hydrogenated block copolymer (b1-2).

The obtained hydrogenated block copolymer (b1-2) had a styrene content of 12% by mass, a butadiene block portion having a vinyl bond content of 81%, a weight average molecular weight of 189,000, a coupling ratio of 55%, a hydrogenation rate of 98.5% and an MFR of 2.5 g / 10 minutes.

The results of the analysis of the obtained hydrogenated block copolymer (b1-2) are shown in Table 1.

(Hydrogenated block copolymer (b1-3))

Li was added in an amount of 0.095 parts by mass based on 100 parts by mass of all the monomers, 0.65 mole of TMEDA was added per mole of Bu-Li, and the amount of styrene in the first step and the third step was changed to 9 parts by mass , The same procedure as in the above-mentioned hydrogenated block copolymer (b1-1) was carried out except that the butadiene content in the second step was changed to 82 parts by mass and the temperature during polymerization was controlled to 67 ° C to prepare a block copolymer, To prepare a hydrogenated block copolymer (b1-3).

The obtained hydrogenated block copolymer (b1-3) had a styrene content of 18% by mass, a butadiene block portion having a vinyl bond content of 55%, a weight average molecular weight of 121,000, a molecular weight distribution of 1.05, a hydrogenation rate of 99.0% and an MFR of 4.0 g / 10 minutes.

The results of the analysis of the obtained hydrogenated block copolymer (b1-3) are shown in Table 1.

(Hydrogenated block copolymer ((b2): b2-1))

Batch polymerization was carried out by using a stirrer having a volume of 10 L and a jacketed reactor.

First, 1 L of cyclohexane was added. Thereafter, 0.065 part by mass of n-butyllithium (hereinafter referred to as Bu-Li) was added to 100 parts by mass of the entire monomers, and N, N, N ', N'- 1.5 mol of ethylenediamine (hereinafter referred to as TMEDA) per 1 mol of Bu-Li and 0.05 mol of sodium t-pentoxide (hereinafter referred to as NaOAm) were added to 1 mol of Bu-Li.

As a first step, a cyclohexane solution (concentration 20% by mass) containing 6.5 parts by mass of styrene was added over 5 minutes, and then the mixture was further polymerized for 5 minutes. During the polymerization, the temperature was controlled at 60 占 폚.

Next, as a second step, a cyclohexane solution (concentration 20% by mass) containing 82 parts by mass of butadiene was added over 60 minutes, followed by further polymerization for 5 minutes. During the polymerization, the temperature was controlled at 55 占 폚.

Next, as a third step, a cyclohexane solution (concentration 20% by mass) containing 6.5 parts by mass of styrene was added over 5 minutes, and then the mixture was further polymerized for 5 minutes.

Next, the fourth step was added, and 5 parts by mass of butadiene was added over 5 minutes, and then the mixture was further polymerized for 5 minutes. During the polymerization, the temperature was controlled at 60 占 폚.

The resulting block copolymer had a styrene content of 13 mass%, a vinyl bonding amount of the butadiene block portion corresponding to the polymer block (B2) of 77%, a vinyl bonding amount of the butadiene block portion corresponding to the polymer block (B-2) of 76% A molecular weight of 174,000, and a molecular weight distribution of 1.09.

Subsequently, the hydrogenation catalyst was added to the obtained block copolymer in an amount of 100 ppm as titanium per 100 parts by mass of the block copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 占 폚.

Then, methanol was added, and then 0.3 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to the block copolymer.

The obtained hydrogenated block copolymer (b2-1) had a hydrogenation rate of 99.0% and an MFR of 5.0 g / 10 min.

The results of the analysis of the obtained hydrogenated block copolymer (b2-1) are shown in Table 1.

(Hydrogenated block copolymer b3)

A polymer having the following structure was used as the hydrogenated block copolymer (b3) in the same manner as described in JP-A-9-327893.

Styrene block amount: 10 mass%, styrene / butadiene random copolymer block amount: 90 mass%, styrene amount in random part: 5 mass%, vinyl amount in random copolymerization part: 79 mole%, hydrogenation rate: 99 mole% 42.0 million

[Polypropylene]

PP-1: Ethylene-propylene random copolymer

    Nova Tech MF3FQ (MFR: 8 g / 10 min, ethylene content: 2.5 wt%, manufactured by Nihon Polypro)

PP-2: Ethylene / Propylene random copolymer

    Nova Tech EG6D (MFR: 1.9 g / 10 min, ethylene content: 1.3 wt%, manufactured by Nihon Polypro)

[Examples 1, 1-1, 2 to 17], [Comparative Examples 1 to 8]

(Production method of film)

Each of the layers shown in Tables 2 to 4 was laminated by a multilayer extruder (Plastic Kagaku Kyushu Co., Ltd., PLABOR Co., Ltd.) in the order described in Tables 2 to 4 (outer layer, ) Under the conditions of an extrusion temperature of 230 占 폚 and a die temperature of 250 占 폚 to obtain a multilayer film having a thickness of 0.25 mm.

[Examples 18 to 24], [Comparative Examples 9 to 15]

Extrusion temperature 230 占 폚 and die temperature 250 占 폚 using a multilayer extruder (PLAGOR, manufactured by Plastic Kogaku Kyukyusho Co., Ltd.) using the materials shown in Table 6, and with the outer layer, And a single layer film having a thickness of 0.20 mm was obtained.

Examples and Comparative Examples The characteristics of the film and the medical container are shown in Tables 2 to 6 below.

This application is based on Japanese Patent Application (Japanese Patent Application No. 2015-177932) filed with the Japanese Patent Office on Sep. 9, 2015, the content of which is incorporated herein by reference.

The film of the present embodiment can be used as a stretch tape used for various medical (clothing) type packaging, various food packaging, household goods packaging, industrial material packaging, various rubber products, resin products, laminates such as leather products, Sheet products such as industrial products such as dicing films, protective films used for protecting construction materials and steel sheets, substrates for adhesive films, trays for food and meat carriers, food and beverage packs and frozen food containers, household appliances such as televisions, stereos and vacuum cleaners Waterproof, waterproof sheet, earth packing, daily necessities, leisure articles, toys, industrial goods, furniture articles, writing tools, transparent pockets, holders, Such as a cover for a file or the like, or a medical instrument such as a liquid bag, and the like. In particular, it can be preferably used as a film for medical treatment and a packaging material such as a food packaging material and a medical (packaging) material.

Claims (13)

At least an outer layer, an intermediate layer and an inner layer,
Wherein said outer layer comprises a polypropylene resin,
Wherein the intermediate layer comprises a polypropylene resin and a hydrogenated block copolymer (a)
Wherein the inner layer comprises a polypropylene resin,
The hydrogenated block copolymer (a)
A polymer block (C) mainly comprising a conjugated diene compound,
A polymer block (B) mainly comprising a conjugated diene compound,
The polymer block (S) containing a vinyl aromatic compound as a main component
Lt; / RTI &gt;
Wherein the content of the polymer block (C) having the conjugated diene compound as a main component in the hydrogenated block copolymer (a) is 1 to 30 mass% and the content of the polymer block (B) containing the conjugated diene compound as the main component is 69 To 98% by mass, the content of the polymer block (S) containing the vinyl aromatic compound as a main component is 1 to 20% by mass,
Wherein the amount of the vinyl block before hydrogenation of the polymer block (C) mainly composed of the conjugated diene compound is 1 to 25 mol%, the amount of vinyl bonds of the polymer block (B) mainly composed of the conjugated diene compound before hydrogenation is 60 to 100 mol% Wherein the hydrogenated block copolymer (a) has a hydrogenation rate of 80 mol% or more,
film. The hydrogenated block copolymer according to claim 1, wherein the content of the polymer block (C) having the conjugated diene compound as a main component in the hydrogenated block copolymer (a) is 3 to 13 mass% ) Is 74 to 96 mass%, the content of the polymer block (S) containing the vinyl aromatic compound as a main component is 3 to 13 mass%
The total content of the polymer block (C) containing the conjugated diene compound as a main component and the polymer block (S) containing the vinyl aromatic compound as a main component is 6 to 26% by mass,
Wherein the hydrogenation block copolymer (a) has a hydrogenation rate of 90 mol% or more. At least an outer layer, an intermediate layer and an inner layer,
Wherein said outer layer comprises a polypropylene resin,
Wherein the intermediate layer comprises a polypropylene resin and a hydrogenated block copolymer (a)
Wherein the inner layer comprises a polypropylene resin,
Wherein the content of the vinyl aromatic compound monomer unit in the hydrogenated block copolymer (a) is 3 to 13 mass%
Wherein the hydrogenation block copolymer (a) has a hydrogenation rate of 90 mol%
The amount of butylene and / or propylene in the hydrogenated block copolymer (a) is 60 to 85 mol% based on 100 mol% of the total of the conjugated diene compound units,
The hydrogenated block copolymer (a) has a peak of crystallization at 0 to 60 캜,
Wherein the hydrogenated block copolymer (a) has a crystallization calorie of 1.0 to 8.0 J / g,
Wherein the hydrogenated block copolymer (a) has a Shore A hardness of 25 to 55,
film. 4. The film according to any one of claims 1 to 3, wherein the thickness of the outer layer is 5 to 50 mu m, the thickness of the intermediate layer is 100 to 200 mu m, and the thickness of the inner layer is 5 to 50 mu m. The method according to any one of claims 1 to 4, wherein the outer layer comprises the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the block copolymer (b1) (Hereinafter referred to as &quot; polymer block (C) &quot; containing no compound as a main component)
Wherein the hydrogenated block copolymer (b1) comprises a polymer block (B1) composed mainly of a conjugated diene compound and a polymer block (S1) composed mainly of a vinyl aromatic compound,
Wherein the content of the polymer block (B1) having the conjugated diene compound as a main component in the hydrogenated block copolymer (b1) is 75 to 92 mass%, the content of the polymer block (S1) containing the vinyl aromatic compound as the main component is 8 To 25% by mass,
Wherein the hydrogenated block copolymer (b1) has a hydrogenation degree of not less than 80 mol%, and the hydrogenated block copolymer (b1) has a hydrogenation amount of not less than 40 mol%
The content of the polypropylene resin in the outer layer is 60 to 100 mass%
Wherein the content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the outer layer is 0 to 40 mass%
film. The hydrogenated block copolymer according to any one of claims 1 to 4, wherein the inner layer comprises the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the block copolymer (b1) The polymer block (C) containing a diene compound as a main component)
Wherein the hydrogenated block copolymer (b1) comprises a polymer block (B1) composed mainly of a conjugated diene compound and a polymer block (S1) composed mainly of a vinyl aromatic compound,
Wherein the content of the polymer block (B1) having the conjugated diene compound as a main component in the hydrogenated block copolymer (b1) is 75 to 92 mass%, the content of the polymer block (S1) containing the vinyl aromatic compound as the main component is 8 To 25% by mass,
Wherein the hydrogenated block copolymer (b1) has a hydrogenation degree of not less than 80 mol%, and the hydrogenated block copolymer (b1) has a hydrogenation amount of not less than 40 mol%
The content of the polypropylene resin in the inner layer is 50 to 95 mass%
Wherein the content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the inner layer is 5 to 50 mass%. The hydrogenation catalyst according to any one of claims 1 to 6, wherein the hydrogenated block copolymer (a)
(A) in the polymer block (B) containing at least two polymer blocks (B) containing the conjugated diene compound as a main component and having the conjugated diene compound as a main component, Wherein the content of the polymer block (B-1) is 1 to 10% by mass of the hydrogenated block copolymer (a)
film. The method according to any one of claims 1 to 7, wherein the outer layer further comprises a hydrogenated block copolymer (b2)
Wherein the hydrogenated block copolymer (b2) comprises a polymer block (B2) composed mainly of a conjugated diene compound and a polymer block (S2) composed mainly of a vinyl aromatic compound,
Wherein the content of the polymer block (B2) mainly composed of the conjugated diene compound in the hydrogenated block copolymer (b2) is 75 to 92 mass% and the content of the polymer block (S2) composed mainly of the vinyl aromatic compound is 8 To 25% by mass,
Wherein the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%, and the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%
The hydrogenated block copolymer (b2)
(B2) in the polymer block (B2) containing at least two polymer blocks (B2) composed mainly of the conjugated diene compound in the molecule, and having a conjugated diene compound as a main component, Wherein the content of the polymer block (B-2) is 1 to 10% by mass in the hydrogenated block copolymer,
film. 9. The resin composition according to any one of claims 1 to 8, wherein the inner layer further comprises a hydrogenated block copolymer (b2)
Wherein the hydrogenated block copolymer (b2) comprises a polymer block (B2) composed mainly of a conjugated diene compound and a polymer block (S2) composed mainly of a vinyl aromatic compound,
Wherein the content of the polymer block (B2) mainly composed of the conjugated diene compound in the hydrogenated block copolymer (b2) is 75 to 92 mass% and the content of the polymer block (S2) composed mainly of the vinyl aromatic compound is 8 To 25% by mass,
Wherein the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%, and the hydrogenated block copolymer (b2) has a hydrogenation rate of not less than 80 mol%
The hydrogenated block copolymer (b2)
(B2) in the polymer block (B2) containing at least two polymer blocks (B2) composed mainly of the conjugated diene compound in the molecule, and having a conjugated diene compound as a main component, Wherein the content of the polymer block (B-2) is 1 to 10% by mass in the hydrogenated block copolymer,
film. The film according to any one of claims 1 to 9, wherein the hydrogenated block copolymer (a) has a weight average molecular weight (Mw) of 100,000 to 300,000. The hydrogenated block copolymer according to any one of claims 1 to 10, wherein the hydrogenated block copolymer (a) has a weight average molecular weight (Mw) of 100,000 to 300,000 and a weight average molecular weight (Mw ) And the number average molecular weight (Mn) (Mw) / (Mn) is 1.01 to 1.30. 12. The method according to any one of claims 1 to 11, wherein the integral elution amount at -20 占 폚 or less as measured by cross fractionation chromatography (CFC) is 0.1% or more and less than 40% Wherein an integral elution amount in the range of not less than 60 占 폚 is not less than 20% and not more than 95% of the total integral elution amount and an integral elution amount in a range of not less than 60 占 폚 and not more than 150 占 폚 is not less than 5% . 13. The method according to any one of claims 1 to 12, wherein the molecular weight distribution (Mw / Mn) of the eluted component in the range of 10 占 폚 or more and less than 60 占 폚 as measured by cross fractionation chromatography (CFC) is 1.05 or more and 1.50 or less , film.